Vulcanizable copolymers of acrylonitrile, butadiene, and vinyl ethers



Patentea Mar. 9, 1948 VULCANIZABLE COPOLYMERS NITRILE, BUTADIENE. AND

OF ACRYLO- VINYL ETHERS Gaetano F. DAlelio, Northampton, Masa, assignor to Pro-phy-lao-tio Brush Company, Northampton, Masa, a corporation of Delaware No Drawing.

This invention relates to new polymerization products and the discovery that a mixture of a butadiene-L3, an acrylonitrile and a monovinyl ether can be copolymerized to form novel copolymerization products which are heat convertible and vulcanizable. Useful articles can be formed from thesecopolymers by molding, extrusion, or calendering. The properties of these new copolymel's depend pon the relative proportions of the ingredients from which they are made. Thus, it is possible to prepare rubber-like compositions .when the butadiene is the major component or resinous compositions when the acrylonitrile is the major component. The. monovinyl ether appears to serve as an internal plasticizer.

When an acrylonitrile is used in an amount of about 35 percent or more, the resulting copolymer has a high softening point and is diflicult to process by customary methods. In such cases, the copolymer may e p ocessed by the method described and claimed in my copending application, Serial No. 523,901 filed Feb. 25, 1944 now U.

S. Patent No. 2,425,086. The process described in that application comprises forming a workable cohesive gel of the copolymer by mixing with certain liquids, such as nitromethane. If a vulcanizable composition is desired, the vulcanizing ingredients may be incorporated in the gel. The gel may be shaped to any predetermined form by extrusion, calendering or the like. Certain of these copolymers may also be improved as to physical properties by cold drawing according to the methods explainedand claimed in said application.

In the practice of the invention, I may use a butadiene-l,3 having the formula hydrocarbon, such Application February 25, 1944, Serial No. 523.900

7 Claims. (Cl. MIL-84.5)

dime-1,3; 2,3-dipheny1 butadiene-1,3; pentadiene-1,3; etc.

In the practice or the invention I may use an acrylonitrile of the structure CH2=CRCN wherein R is hydrogen or a methyl radical.

The monovinyl ethers used in the practice 01' this invention possess the general formula CHa=CH-OR' wherein R represents the residue of a monohydroxy alcohol; the only requirement 01' the alcohol is that it is devoid of ethylenic and acetylenlc unsaturation.

As examples of alcohols fromvwhich the ethers may be prepared, I may use methyl, ethyl. propyl. isopropyl, butyl, isobutyl, amyl, secondary amyl, isoamyl, mixed amyl, hexyl, cyclopentyl, cyclohexyl, methyl cyclopentyl, methyl cyclohexyl. benzyl, phenethyl, chloroethyl, acetoxyethyl. methoxyethyl, ethoxyethyl, butoxyethyl, phenoxyethyl, chlorphenoxyethyl, acetoxypropyl. methoxypropyl, ethoxypropyl, phenoxypropyl, carbalkoxyethyl, etc., alcohols.- The term monovinyl ethers as hereinafter used. refers to the ethers of monohydric alcohols as mentioned above and does not embrace unsaturated ethers possessing another polymerizableethylenic or acetylenic group. Vinyl ethers containing 2 to 6 carbon atoms in the R group are to be preferred,

I am also aware that copolymers of acrylic nitriles with moncvinyl ethers have previously been known. As a typical example, mention my be made of the acrylonitriJe-vinyl ethyl ether copolymers. These copolymers are thermoplastic.

non-vulcanizable compositions which possess the structure according to the reaction as follows:

where the numerical values or "n" and "m'? depend on the mol ratios used. Such copolymers are thermoplastic and soluble and as far as I have been able to ascertain have not been converted to the insoluble, iniusi-ble state. Furthermore, such copolymers are prepared with extreme diillculty.

Copolymers of vinyl ethers and 1,3-dienes are also dimcult to prepare. and in fact, when attempts are made to copolymerize low quantities of vinyl ether, of the order of to 40%, with butadiene, the vinyl ether exhibits an inhibiting efiect on the polymerization of the butadiene.

I am likewise aware that copolymers of acrylonitrile' and butadiene are known. However, in many respects, these copolymers are not satisfactormas in the difilculty encountered in processing the copolymer, and in that the material is inferior to other natural and synthetic resins at low temperatures. Many of these difliculties are either lessened or eliminated by the practice of this invention.

In view of the above chemical reactions, it is surprising that tripolymers of predetermined composition can be prepared when the polymerizable ingredients of a mixture comprise a dime- 1,3; an acrylic nitrile; and a monovinyl ether.

Many advantages accrue to the practice of my invention. By its use it is possible to prepare internally plasticized synthetic rubber compositions when the butadien component is in the major proportion, thereby contributing added properties to an acrylonitrile-butadiene polymer by a direct copolymerization process with a vinyl ether. This isevidenced by the greater ease with which the copolymer of acrylonitrile, vinyl butyl ether, and I vent resistance and their toughness. Such compositions possess greater ductility than the corresponding composition of acrylonitrile and butadiene from which the ether has been omitted in the polymerization process.

It is thereby seen that .the compositions of this invention possess a greater utility than it is possible to achieve by polymerizing separately (1) the acrylonitrile with the butadiene, (2) the acrylonitrile with the'vinylether, or (3) the vinyl ether with the butadiene. Example 1 indicates the wide range of polymers that may be obtained in the practice of this invention. I

The objects of this invention are achieved by emulsion polymerization of a mixture comprising the ratios of 30 to 90 parts of the acrylonitrile; 2 to 70 parts of the butadiene-1,3; and 2 to 40 parts of a monovinyl ether. Depending on the proportions of the ingredients used, compositions suitable as 1) synthetic rubbers or (2) molding compounds which may be used directly in the preparation of molded parts or further treated with vulcanizing or curing agents, are readily prepared.

When prepared by the non-aqueous polymerization methods in conjunction with alkali metal catalysts such as sodium, potassium, calcium, sodium triphenyl methyl, etc., catalysts, the prod- "'ucts are not entirely satisfactory since such catalysts causea considerable portion of the butadiene to cross link whereby the butadiene behaves as a divlnyl instead of reacting according to the 1,4- additlon. When the dienes are polymerized by alkali metals in 'the presence or unsaturated ethers having an oleflnic double bond in the molecule, these ethers behave more in the function of diluents and as controlling media rather than as co-reactants as is evidenced by the fact that when high quantities or oleflnic ethers, for

- ether may act as a retarder of polymerization.

Any suitable method may be used for the preparation of the polymers of this invention; however, emulsion methods are preferred. When the synthetic resins are prepared by emulsion polymerization, any substance may be used as the emulsifying agent which, when dispersed in water con taining the polymerizable and other ingredients, is capable of producing a permanent dispersion of the reactive ingredients in water. The most suitable dispersion or emulsifying agents are those which give stable emulsions throughout the course 01' the polymerization.

Additional examples of emulsifying agents besides the potassium oleate used in Example, 1 are Ivory soap, the sodium salts of sulfonated longchain alcohols, the water-soluble salts of suli'osuccinic esters, N-stearyl betaine, cetyl trimethyl ammonium'bromide, soluble lignin sulionic 'acid salts, C-cetyl betaine, etc. Usually a 2 to 4% solution of an emulsifying agent in water is suitable in the preparation of a good dispersion, but a range 01' 0.2% to 10% may be used when a weaker or stronger solution is desired,

Many of the polymers of this invention may likewise be prepared in granular form and in this case agents are used which have relatively poor dispersing properties whereby they form nuclei for the formation of granules of the tripolymers. Such agents are usually called granulating agents and this process may be defined as the method of preparing these copolymers in granular form which comprises dispersing the polymerizable mixture in water by means of a protective colloid and polymerizing the mixture under agitation. The concentration of the granulating agent or protective colloid is adjusted so that it is not substantially greater than the amount of agent sufllclent to maintain the polymerizable mixture in the dispersed phase while agitation is maintained and sufficient to prevent adhesion or coagulation of the dispersed particles during the polymerization process.

Examples of such protective colloids and granulating agents are soluble starch, methyl starch, polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, gelatin, sodium halogenate soluble salts of cellulose, glycolate soluble salts of starch, glycol soluble salts of polyvinyl alcohol glycolate, polymethacrylic acid, natural gums, etc.

Usually a concentration of 0.1 to 1% of agranulating agent in water is satisfactory. The quantities, however, are adjusted to the dispersing power of the protective colloid.

As catalyst for the polymerization I may use any eifective oxygen liberating agent such as benzoyl peroxide, sodium persulfate, potassium peralyst and upon the desired rate of olymerization.

The course of polymerization of the monomeric mixture used in the properties of the polymers of this invention may be modified considerably by the presence of other ingredients used to modify or control the reaction. Thus, I may use small amounts of sulfur; hydroquinone; copper, naph-- thyl amine; carbon tetrachloride; pyrogallol: the higher mercaptans; the thiurams; the dithiurams; ferrous and ferric salts such as the tartrates, citrates, lactates; finely dispersed metals; halogenated amides; etc.

The ratio of the dispersed phase, that is, the mixture of the polymerizable monomers, to the water used with the emulsifying agent or protective colloid as the dispersing phase, may be varied widely. Satisfactory results are obtained in the range of 100 parts of monomer mixture to 100-500 parts of the dispersing phase. Auxiliary organic solvents such as dioxane, ethyl alcohol, glycols, benzene, etc. may likewise be used in the presence of the dispersed and dispersing phases. These ingredients may be added directly to the polymerizable mixture or maybe present as diluents in the reacting ingredients. Thus, the'butadiene, as prepared by the catalytic dehydrogenation of the butenes, may contain some butane as well as some butene-l and butene-2. Likewise, the 'acrylonitrile may contain definite quantities of lactonitrile or methacrylonitrile. The monovinyl ether.

may likewise contain small quantities of alcohol.

The fundamental resins of this invention likewise may be modified by other polymerizable monomers containing a single-ethylenic polymerizable double bond. Illustrative examples of such compounds are the vinyl halides, e. g., vinyl chloride; the vinylidene halides, e. g., vinylidene chloride, vinylidene fiuorochloride, etc.; the esters of acrylic acid, e. g., methyl acrylate, ethyl acrylate, ethyl methacrylate, methylmethacrylate, methyl chloracrylate, fluorophenyl acrylate, etc.; the substituted aryl ethylenes, e. -g., bromotoluyl ethylene, etc.; the vinyl esters, e. g., vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate; the nitrile derivatives of acrylic and methacrylic acid, e. g.. acrylonitrile, methacrylonitrile, etc.; methylene malonic esters; the monoalkyl esters, e. g., the methyl ester; the diesters, e. g., the dimethyl ester, the dipropyl ester, etc.; the allyl derivatives, e. g., acroleln, methacrolein, vinyl methyl ketone, vinyl ethyl ketone, allyl chloride, dimethyl maleate, diethyl maleate, diethyl fumarate, allyl phenyl ether, allyl acetate, allyl propionatc, allyl benzoate, etc.

In any of the above polymerization methods, the reaction may be carried out conveniently at to C. within a few days depending on the composition of the ingredients, the amount of catalyst, etc. It is possible with higher catalyst concentrations or with increased temperatures to decrease the reaction time to five to seven hours.

When the gaseous derivatives of butadiene-1,3 are used, the higher temperatures are to be avoided. The choice of the polymerization temperature, as, is readily seen, depends on the choice of ingredients. of catalyst, of ratio of the dis- The emulsified or dispersed polymers may be coagulated by any of the methods applicable to the dispersed polymer relative to the particular emulsifying or dispersion agent used. In many cases solutions of aluminum sulfate are satisfactory when added slowly and with stirring. Sodium chloride solutions, preferably those containing free acids such as sulfuric, hydrochloric, or acetic acid, are preferable because of low cost. Alternately, the emulsion may be broken by freezing or heating, thereby eliminating the addition of foreign or electrolytic material to the polymer. In many cases the addition of a lower alcohol such as methyl or ethyl alcohol satisfactorily breaks the emulsion. I

In the ordinary method of producing granular polymers, precipitants are not usually required, but should a small amount of emulsion be obtained with the granular product, the resin contained in the emulsion may be precipitated by any of the means mentioned above.

In many cases where films or molded products of the copolymers of this invention are to be used unvulcanized and are required to withstand prolonged aging, it is desirable to add a small amount of antioxidant to such compositions con taining high amounts of acrylic nitrile which are intended for use as unvulcanized thermoplastics.

It is obvious that the compositions of this in.- vention made with high quantities of butadiene should likewise be compounded withantioxidants and inhibitors to give them strength before their use in producing vulcanized products.

As suitable oxidation inhibitors may be mentioned N-phenyl beta naphthyl amine, hydroquinone, eugenol, and similar substances, the amount needed being small, of the order of 0.1 to 2% of the weight of the inter-polymer.

Many of the copolymers of this invention, are soluble in the nitrohydrocarbon solvents and, as such, are well adapted as film-forming materials, etc. These solutions may be used with or without vulcanizing or curing agents. When made in suitable equipment and under favorable conditions, thefilms are practically colorless. Furthermore, they are strong, tough, and flexible. Adhesion of these films to base materials such as wood, metal, glass, and the like is excellent. Such unpigmented solutions are useful as clear varnishes, lacquers, coating compositions, adhesives,

etc., whereas the pigmented solutions are suitable for coating compositions such as paints, and pigmented lacquers for wood, metal, paper, leather, cloth, cork, asbestos board, etc.

Unpigmented copolymer solutions or emulsions of the copolymer are suitable for impregnating or coating papers and textiles, cellular and other fibrous bodies, and porous or semi-porous materials to contribute to their strength, toughness, imperviousness to moisture, flexibility, etc.

The molding composition-s prepared from such bodies, particularly those of a plastic nature persed to the dispersing phases, and the type of equipment employed.

rather than a rubber-like nature possess the ability to withstand bending pressures when such pressure is applied slowly. These tripolymers are ideally suited for the preparation of articles that are usually subjected to bending strains such as in combs, or wiring of electrical equipment, panel boards, leather, etc.

The polymers of this invention containing in general 50 or more percent of butadiene in the copolymer are rubber-like while the polymers containing less than 50% of, butadiene are of the nature of ductile synthetic resinous compositions capable of being vulcanized in the usual of potassium persulfate in the presence of 0.5 part of steel wool as an activator and moderator of the reaction. The polymerizable mixture is inmade by copolymerizing a mixture of about 30 to 40 parts of an acrylonitrile, 55 to 70 parts of a butadieiie-L3 and 2 to 10 parts of a monovinyl ether, while a resin-like product may be made by copolymerizing a. mixture of about 50 to 90 parts of an acrylonitrile;2 to 30 parts of a butadiene.-1,3 and 2 to 40 parts of a monovinyi ether.

The compatibility of these new compositions with plasticizers 'is higher than that or the normal acrylonitrile-butadiene composition. This is attributed to the fact that the ether which has nterpolymerized with the other ingredients, ifers wider possibilities in the selection of. suitable plasticizers.

Among the plasticizers suitable for use in this invention are dimethyl phthalate, diethyl phthalate, tricresyl phosphate, dibenzyl sebacate, dibutyl sebacate, diethylene glycol dihexoate, dibutoxyethyl sebacate, dicrotyl azeleate, tributyl citrate, chlorinated diphenyls, triacetone, tetraethylene, octyl phthalate, cyclohexyladipate, benzyl borate, dibenzyl ether, octyl chlorbenzoate, glycerol trilevulinate, ethylene glycol butyl phthalate, tetrahydrofurfuryl. sebacate, tetrahydrofurfuryl fumarate, tributyl aconitate, etc. A wide variety or plasticizers may be used because of the solvation eifect of the ether in the tripolymer.

The fundamental resins of this invention may be likewise compounded with other synthetic resins and other synthetic rubbers. They may be blended with the unsaturated alkyl resins, plasticized polyvinyl chloride resins, the polyvinyl acetal resins, with pigments, fillers, dyes, lubricants, softeners, etc.

The vulcanization of these polymers may be accomplished in the standard method of vulcanizing natural or synthetic rubber with or without reenforcing agents such as carbon black, etc.

As accelerators in conjunction with sulfur, there may be used the aldehyde amines, the guanidines, the carbon disulfide derivatives or mixtures of such materials, Some typical examples are heptaldehyde-aniline, butyraldehyde butyl amine, diphenylguanldine, di-o-toluylguanidine, triphenylguanidine, zinc dimethyl dithiocarbamate, zinc dibutyl dithiocarbamate, tetramethyl thiuram, disulfide, tetramthyl thiuram monosulfide, mercapto benzothiazole, zinc mercaptobenzothiazole, benzothiazole disulfide, etc.

These materials may also be vulcanized without sulfur through the use of nitro compounds and organic peroxides such as trinitrobenzene, tetranitronaphthylene, benzoyl peroxide, a mixture of benzaldehyde and mercuric oxide, halogenated benzoquinones, benzoquinone dioxime, etc.

Other fillers and reenforcing agents and diluents may beused, such as wood flour, cotton flock, alpha flock, mica, asbestos, silica, powdered quartz, bagasse, lignocellulose, hydrolyzed wood,

Example 1 The following compositions are suitable for emulsion polymerization using the ratio of 25 parts of polymerizable monomer to about 50 parts of 5% potassium oleate solution in distilled water. As polymerization catalyst there is used 0.25 part troduced into pressure vessels and reacted at 50' C., for at least 12 hours. An oxidation inhibitor, namely, N-phenyl beta. naphthyl amine, is added to the resulting latex before precipitation with an aqueous 5% sodium chloride solution containing 2% sulfuric acid. The granulated polymers are washed free of soluble material, dried in a vacuum oven, and milled on rolls. The ratio of the polymerizable components is given in the following table:

Specimen Acrylonitrile l 'hfi' f Butadiene 30 10 60 40 10 5O 5O 10 40 60 10 30 60 20 20 60 3O 10 70 1 5 15 so 5 15 10 10 so 15 5 All of the above polymers were vulcanizable even those containing small quantities of butadiene. The types of polymer obtained are:

Specimen Characteristics A Rubbery, very elastic, high elongation. TL. Rubbery, less elastic than A. (7.- Ductile, vulcanizablc which yields readily on bending l) Similar to C but less yielding. E" Similar to C. F. Touch, more yielding than E. G. Tough, more ductile than F. 11.. Tough, harder than G. I... Very tough. harder than H. J Tough, softer than and similar io'I.

Example 2 Vulcanized products of high utility are obtained by processing samples B, D, E and F using the following as the ratio of components:

Parts Tripolymer Carbon black I 25 Zinc nxirlp 5 Benzothiazyl disulfide 2 Sulfur 2 Steario acid 1 Example 3 A varnish solution of tripolymer of specimen J is prepared by dissolving the tripolymer in benzene to give a 20 to 30% solution and adding one part of benzothiazyl disulfide and two parts of sulfur. This varnish solution is used directly as a vulcanizable coating for wood, glass, and as an impregnant and coating .for paper, fabric, etc. The adhesion in all cases, even the adhesion to glass, is excellent.

Example 4 The following example gives a typical formula for the preparation of synthetic rubber:

Parts Butadiene 1137 Acrylonltrile 502 Vinyl butyl ether '78 Distilled water 3500 Potassium oieate 87.0 Potassium persulfate 8.75 Ferric citrate (or phosphate) 8.0 Higher allnvl mercaptan 5.0

which are reacted from 7-9 hours at 50 to 55 C.,

'at'which time 37 parts of N -phenyl beta naphthyl The following ingredients were reacted for 24 hours at 65 to 70 C., in a steam-jacketed reactor equipped with stirrer, etc.

Parts Dioctyl ester of sodium sulfosuccinic acid Distilled water 500 Acrylonitrile 60 2-methyl pentadiene-1,3 20 Vinyl butyl ether 20 Potassium persulfate 0.5

The emulsion was precipitated using a 3% hydrochloric acid solution saturated with sodium chloride. The precipitate was washed in boiling water to remove chlorides and then dried in a vacuum oven under 24 inches of mercury at 50 C. An almost theoretical yield of a tough, flexible, vulcanizable copolymer was obtained.

Example 6 Other modifications as to ratios other than in Example 1 may be prepared as follows, using a trace of iron as an activator.

Vinyl Specimen Butadiene Copolymcr 5 65 Rubbery. 29.2 53. 5 17. 5 Elastic, tough 75 12. 5 l2. 5 Hard, tough.

What I claim as new and desire to secure by- Letters Patent of the United States is:

1. A composition comprising the polymerization product of a mixture comprising 30 to 90 parts of a compound selected from the group consisting of acrylonitrile and methacrylonitrile, 2 to 70 parts of a butadiene-1,3 having the forenic and acetylenic unsaturation, the major component oi said mixture being selected from the group consisting of said acrylonitriles and said butadiene.

2. A composition comprising the polymerization product of a mixture comprising 30 to parts of a compound selected from the group consisting of acrylonitrile and methacrylonitrile, 2 to 70 parts of a butadiene-1,3, having the formula where R is a radical selected'irom the group consisting of hydrogen, alkyl, aryl, and cycloaliphatic radicals which are free of ethylenic unsaturation, and 2 to 40 parts of a vinyl butyl ether, the major component of said mixture being selected from the group consisting of said acrylonitriles and said butadiene,

3. A rubber-like composition comprising the polymerization product of a' mixture comprising 30 to 40 parts of a compound selected from the group consisting of acrylonitrile and methacrylonitrile, 55 to 70 parts of a butadiene-l,3 having the formula where R is a radical selected from the group consisting of hydrogen, alkyl, aryl, and cycloaliphatic radicals which are free of ethylenic unsaturation and 2 to -10 parts of a monovinyl ether having the structure CH2=CHOR' where R is a hydrocarbon radical having not more than 6 carbon atoms and which is free of ethylenic and acetylenic unsaturation.

4. A rubber-like composition comprising the polymerization product of a mixture of 1137 parts of butadiene-1,3,- 502 parts acylonitrile and 78 parts of vinyl butyl ether.

5. The product resulting from the vulcanization of the polymerization product of a mixture comprising 30 to 90 parts of a compound selected from the group consisting of acrylonitrile and methacrylonitrile, 2 to 70 parts of a butadiene-L3 having the formula the polymerization product of a mixture compris-- ing 30 to 40 parts of a compound selected from the group consisting of acrylom'trileand methacrylonitrile, 55 to 70 parts of a butadiene-1,3

having the formula where R is a radical selected from the group consisting of hydrogen, alkyl, aryl, and cycloaliphatic radicals which are free of ethylenic unsaturation, and 2 to 10 parts of a monovinyl ether having the structure CHz'=CHOR' where R is a hydrocarbon'radical having not more than 6 carbon atoms ama:

11 l l and which is free of ethylenlc and aoctylcmc 1m- Number '1. The product resulfln: from vulcanization o! 2 m 331 the polymerization product of a mlxturc o! 1187 1 REFERENCES CITED 12 um'rm sum PATENTS Name Date Carothers et a1. Jan. 5, 193! Arnold et a1. Feb. 18, 1941 Btukweather et a1. Mar. 11, 1941 Fryllng Mar. 9, 1948 Fryllnz Aug. 21. 1945 OTHER REF'ERWCEB The tollowin: references are 0! record in the 10 Barron, Modem Synthetic Rubbcm's, published 1110 01 this Mt:

by Van Noatrgnd, N. Y. 1944, me 146. 

